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Publication numberUS4222828 A
Publication typeGrant
Application numberUS 06/045,424
Publication dateSep 16, 1980
Filing dateJun 4, 1979
Priority dateJun 6, 1978
Publication number045424, 06045424, US 4222828 A, US 4222828A, US-A-4222828, US4222828 A, US4222828A
InventorsEduard Zuurdeeg
Original AssigneeAkzo N.V.
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process for electro-codepositing inorganic particles and a metal on a surface
US 4222828 A
Abstract
A process is provided for the electrolytic codeposition of a metal and solid inorganic particles on an article acting as a cathode. The particles have an average size of less than 300μm and are used in a concentration of 10 to 150 grams per liter of plating bath liquid. The inorganic particles are kept suspended in the bath liquid with a cationic fluorocarbon surfactant present in an amount which is at least the same weight ratio to the particles in the bath liquid as the ratio of surfactant to particles required in an 0.005 N KNO3 - solution for the particles to assume a zeta-potential of at least +40 mV. Preferably the surfactant consists of a cationic fluorocarbon compound having the structural formulae: ##STR1##
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Claims(9)
What is claimed is:
1. In a process for the codeposition from an electroplating bath of a metal and solid inorganic particles on an article acting as a cathode, which particles are kept suspended in the bath liquid in the presence of a surfactant and have an average size of less than 300 μm and are used in a concentration of 10 to 150 grams per liter of bath liquid, characterized in that the surfactant is a cationic fluorocarbon compound in at least the same weight ratio to the particles in the bath liquid as in an 0.005 N KNO3 -solution in which the particles assume a zeta-potential of at least +40 mV with the exclusive use of said cationic fluorocarbon compound.
2. The process of claim 1, characterized in that the amount of cationic fluorocarbon compound is equal to that required in a 0.005 N KNO3 solution for the particles to assume a zeta-potential of at least +60 mV with the exclusive use of said cationic fluorocarbon compound.
3. The process of claim 1 or 2, characterized in that the cationic fluorocarbon compound is a compound having one of the following structural formulae: ##STR15##
4. The process according to claim 1 or 2 characterized in that besides solid inorganic particles, solid particles of a different kind are simultaneously deposited.
5. The process according to claim 4, characterized in that the said different kind of solid particles are inorganic particles, too.
6. The process according to claim 4, characterized in that the said different kind of solid particles are organic particles.
7. In a process for electrolytically codepositing a metal and particles of an inorganic compound simultaneously on a cathode which comprises depositing said metal and particles from a bath containing as the only surfactant a cationic fluorocarbon surfactant and the said particles have a zeta-potential of at least +40 mV.
8. The product of the process of claim 7.
9. The process of claim 4 wherein said different kind of particles are organic fluorocarbon particles.
Description

This invention relates to a process for depositing composite coatings containing a metal and inorganic particles from an electroplating bath. More specifically, the invention relates to a process for the codeposition from an electroplating bath of a metal and solid inorganic particles on an article acting as a cathode and to the resulting coated article.

One process of the general type indicated above is described in U.S. Pat. No. 3,891,542. In accordance with the disclosed process, nickel and silicon carbide particles are codeposited electrolytically from an aqueous bath on an article which serves as the cathode. The silicon carbide particles are kept suspended in the bath with the aid of a surfactant such as sodium lauryl sulphate. One disadvantage of the disclosed process is that only a low percentage of particles can be incorporated into the composite layers. A weight percentage of silicon carbide particles of 3 to 5% is disclosed. However, this percentage can only be obtained at a relatively high concentration (90 to 150 grams per liter) of silicon carbide particles in the bath liquid. Other required undesirable conditions are an exceptionally high electrolyte concentration and very vigorous agitation of the bath liquid to retard sedimentation of the suspension and to obtain a sufficiently homogeneous distribution of the particles in the coating.

It is an object of this invention to provide an improved process for the simultaneous electrolytic deposition of a metal and solid inorganic particles such as silicon carbide on a surface of an article acting as a cathode. Another object of the invention is to provide such an electrolytic deposition process which makes it possible to incorporate a larger percentage of the inorganic particles in the resulting coating. Still another object of the invention is to provide improved dispersion of the inorganic particles in the electroplating bath without requiring vigorous agitation.

The present invention provides a process which makes it possible to incorporate substantially higher percentages of solid particles in metal coatings with the use of an electroplating bath having a substantially lower concentration of solid particles and electrolyte without vigorous agitation of the bath.

In accordance with the invention, an electroplating bath is provided which contains a surfactant in the form of a cationic fluorocarbon compound in at least the same weight ratio of surfactant to particles in the bath liquid required in an 0.005 N KNO3 -solution for the particles to assume a zeta-potential of at least +40 mV with the exclusive use of said cationic fluorocarbon compound as the surfactant.

It should be added that the use of a cationic compound for the codeposition from an electroplating bath of a metal and solid inorganic particles on an object which acts as a cathode has been proposed before in the U.S. Pat. No. 3,844,910. An amino-organosilicon compound, for instance gamma-propyltriethoxysilane, is employed in the disclosed bath to promote the incorporation of non-metallic particles such as silicon carbide in a matrix of metal. Although the results obtained with the process are better than those of the previous processes, the percentage of particles incorporated is still insufficient for many purposes.

Moreover, in the case of a particle size of over 10 microns, the amount of nonmetallic particles that can be incorporated by the disclosed process has been found to decrease with increasing average particle size.

The use of a cationic surfactant in the incorporation of solid inorganic particles in a matrix of metal also is disclosed in British Patent Specification No. 1,070,343. The amount of cationic surfactant employed, viz. cetyltrimethylammonium bromide, is only 10 mg per 25 grams of particles and is insufficient to cause the particles to assume a zeta-potential of at least +40 mV in an 0.005 N KNO3 -solution. Moreover, the disclosed surfactant is of the hydrocarbon type, which has a very unfavorable influence on the quality of the electrodeposited coating (ductility).

In the Japanese Patent Specification No. 50-45735, a surfactant of the fluorocarbon type is used in the codeposition from an electroplating bath of gold and abrasion-resistant nonmetallic particles on an article acting as cathode. In the example given in this patent, the incorporation of titanium nitride (TiN) in a coating is carried out with the use of 3 g of surfactant of the fluorocarbon type per 20 g of particles. Hence, the particles used are very small, viz. 0.05 μm, the specific surface area is very large and such a small amount of surfactant will not be sufficient to obtain a zeta-potential in an 0.005 KNO3 -solution of at least +40 mV. Moreover, nothing is said in this patent about the charge of the fluorocarbon surfactant used in the example.

A process is disclosed in U.S. Pat. No. 3,787,294 in which a cationic surfactant of the fluorocarbon type is used in the codeposition from an electroplating bath of a metal and graphite fluoride particles on an article acting as cathode. It is generally known, however, that graphite fluoride particles resemble polyfluorocarbon particles more than they resemble particles whose incorporation forms the subject of the present invention. This U.S. patent can therefore not be considered to contain a general teaching with regard to the incorporation of inorganic solid particles in a metal coating.

For the determination of the surface area of the particles use is preferably made of the nitrogen adsorption method of Brunauer, Emmett and Teller (BET), which is standardized in the German Industrial Standard DIN 66132.

By solid inorganic particles that can be incorporated in accordance with the process provided by the invention are to be understood here not only all particles that are of solid inorganic compounds which are inert relative to the bath conditions, such as the carbides, borides, silicides or nitrides of titanium, zirconium, wolfram, hafnium, niobium, tantalum, chromium, molybdenum, vanadium, and thorium, but also particles of simple or composite metal oxides such as Al2 O3 ; SiO2 ; IrO2 ; Cr2 O3 ; ZrO2 ; PbO2 ; Pb3 O4 ; Al2 O3.2TiO2 ; Beo.Sio2 and ZrO2 Si and the like. To obtain an abrasion-resistant coating, the incorporation of SiC or B4 C particles are preferred. Also, particles of metals or metal alloys can be included in composite metal coatings in accordance with the invention. Also, graphite, sulphur, silicon, diamond, sulphides (such as molybdenum disulphide) and silicates (talc, mica) can be codeposited with a metal in accordance with the invention.

The percentage of inorganic particles that may form a part of composite coatings when use is made of the process provided by the invention varies from a few percent say about 3% to the theoretically maximum volume percentage of about 70%. It has been found that the smaller the particles the more of them can be deposited from the same amount by weight per liter of bath liquid.

The process of the invention can be used for depositing the same metals as those which can be deposited from an electroplating bath by the prior art processes. As examples of these metals may be mentioned silver, iron, lead, nickel, cobalt, cadmium, copper, zinc and metallic alloys such as bronze, brass and the like.

In addition to solid inorganic particles, the electroplating baths used in the process according to the invention may contain particles of some other inorganic or organic material. As an example, a combination of SiC, MoS2 and Pb-oxide+PTFE* may be codeposited. Of particular importance are resinous particles of, inter alia, polyfluorocarbon compounds, polyvinyl chloride, polyvinylidene chloride, polyolefins, polyesters, polystyrene, polyacrylates, polyamides, polyimides, aromatic polyamides and polyurethanes. If use is made of such combination of different particles it is advisable as much as possible to choose the same particle size.

The preparation of the dispersions to be employed in the present process may be carried out in any convenient manner. It may be effected by adding the calculated amount of cationic surfactant to the electroplating bath in which the envisaged particles have been taken up or, as is preferred, first adding the wetting agent to a very strongly agitated, concentrated suspension of the particles to be occluded and subsequently adding the resulting suspension to the electroplating bath.

Particularly in the simultaneous incorporation of resinous particles, it is very much advisable that the various dispersions should be prepared separately prior to their being added to the electroplating bath.

In the process according to the invention, use should be made of cationic surface active fluorocarbon compounds such as those having one of the following structural formulae: ##STR2##

Of the above compounds, the last-mentioned one is to be preferred because it is a surfactant that gives the most favorable results. In view of the possibility of electrochemical oxidation and precipitation, it is preferred that the anion of the lastmentioned compound be replaced with a Cl- or SO4 2- ion.

Under some circumstances, it may be desirable for the electroplating bath also to contain a stress reducing agent, such as p-toluenesulphonamide or saccharin.

The invention will be further described in the following examples, which are all directed to the codeposition from an electroplating bath of a metal and solid inorganic particles of various chemical compositions and particle sizes. First of all, a description will be given of the general conditions used in the examples, after which the results of the experiments will be summarized in a number of tables.

The experiments, according to the process of the invention, were carried out with the use of a cationic fluorocarbon-containing surfactant. For comparison, experiments also were carried out in the presence of a cationic surfactant not containing a fluorocarbon chain, viz. a surfactant of the hydrocarbon type.

Measurement of zeta-potential

Preparatory to the experiments, first the zeta-potential of the solid inorganic particles to be incorporated by electrodeposition was measured as a function of the amount of surfactant. This was done in order to determine at what amount of surfactant the particle potential exceeded +40 mV. In the actual experiments in the electrolyte bath, a somewhat larger amount of surfactant was used than the amount thus determined. Moreover, in Example I, experiments were carried out with the same surfactant in two concentrations that were lower than the determined amount. The measurement of the zeta-potential was so carried out that as far as possible, the same concentrations of the solid inorganic particles in the aqueous dispersions were used as those that were to be employed in the electroplating bath.

In 350 ml-beakers, a series of dispersions were prepared, one of them consisting of 121/2 grams of solid inorganic particles and 250 ml of demineralized water. The other dispersions of the series contained varying amounts of surfactant as well as 121/2 g of solid inorganic particles and 250 ml of demineralized water. For each of the various kinds of particles, a separate series of dispersions were prepared in this way. By "various kinds of particles" are not only to be understood here particles of different chemical compositions, but also those that only differ in particle size. The contents of the beakers were homogenized for 2 minutes with an Ultra Turrax stirrer, type T 45/N of the German firm of Janke and Kunkel A. G., operating at a speed of 10,000 revolutions per minute. Subsequently, the dispersions were allowed to stand for 15 hours to permit the air to escape. Next, the dispersions were stirred with a magnetic stirrer for about 10 minutes without air occlusion and visually inspected then for stability, flocculation symptoms and sedimentation speed. Subsequently, the dispersions were stirred with the magnetic stirrer for about 5 minutes, after which from each beaker 1 ml of the dispersion was taken, which was diluted with 50 ml of an aqueous 0.05%-solution of KNO3 (0.005 N KNO3 -solution).

Of the dispersions thus diluted, the velocity of the solid inorganic particles under the influence of an electric field was measured.

From this velocity, the electric conductivity of the dispersion and the electric field strength, the zeta-potential was calculated. For further particulars about the measurement of the zeta-potential reference is made to "Electrophoresis", Duncan J. Shaw, Academic Press, London, New York, 1969.

In the following Example I, the procedure used in the experiments will be further described. The same procedure, mutatis mutandis, is used in all the other examples. Differences, if any between the examples will appear from the respective tables. In these tables are summarized the various conditions used in the experiments and the results obtained with the experiments.

EXAMPLE I

For the electrolyte bath, use was made of a Watt's nickel plating bath, the solid inorganic particles of silicon carbide having being supplied by Kempten GmbH, Munich, under the name SiC 1200. They are particles having a mesh value of 1200 and an average size of about 5 μm.

A 11/2 liter nickel plating bath was prepared employing the following ingredients:

______________________________________              grams/liter______________________________________NiSo4 . 6H2 O                240NiCl2 . 6H2 O                40H3 BO3     40______________________________________

The pH was 4.2 and the temperature was 52 C.

To this bath there were added 75 grams of SiC1200 and 375 mg of a cationic fluorocarbon surfactant, i.e., 5 mg of surfactant per 1 gram of SiC. The surfactant had the following structural formula: ##STR3##

In a 200 ml-beaker, this mixture was homogenized with an Ultra Turrax stirrer of the type mentioned before at a speed of 10,000 revolutions per minute. Subsequently, the resulting dispersion was gently stirred for one-half hour at a temperature of 52 C. with an IKA Combimag magnetic stirrer to allow the escape of air occluded in the preceding stirring operation.

As could afterwards be established, the dispersion obtained looked moderately stable.

As cathode now a round bar of stainless steel 60 mm long and 4 mm in diameter was hung in the bath contained in the beaker. The bar had been pretreated successively by blasting with granular corundum having a mesh value of 220, rinsing, degreasing with an alkaline detergent, rinsing, activating in a boiling solution of FeCl3 and again rinsing with water.

The anode hanging in the beaker consisted of a nickel plate 1 mm thick, 8 cm high, and 15 cm long and was so bent that it was just touching the inside wall of the beaker. The anode and the cathode were then connected to a current source supplying a direct current of 0.75 A.

So, considering the cylindrical outer surface area of the cathode, the current density was 10 A/dm2. The electrodepositing lasted 15 minutes, the bath being moderately stirred to prevent sedimentation of SiC particles. Next, the cathode and the anode were removed from the beaker, rinsed with water and transferred to a beaker of the same dimensions containing a normal Watt's nickel plating bath (without SiC or surfactant). In this bath, the cathode bar was subjected to a continued electroplating treatment lasting 30 minutes at a current density of 5 A/dm2. As a result, a second coating consisting of nickel was deposited on the composite coating of nickel and silicon carbide formed in the first electroplating step.

Of the bar thus treated, a 15 mm long piece was sawed off and entirely embedded in a solidifying mass. Then the integrated whole of embedding mass and bar was ground off until a semi-cylindrical part of the bar was left, the outer nickel coating serving as a supporting layer. On the fine-ground face, the incorporated darker SiC particles could be very well distinguished from the lighter nickel.

The uniformity of distribution of the SiC particles in the nickel could, therefore, be very well determined visually. The volume percentage of incorporated SiC particles was determined with a Zeiss microvideomat. The experiment was carried out at three different concentrations of surfactant, based on the amount by weight of SiC particles:

a. 5 mg of surfactant per gram of SiC

b. 10 mg of surfactant per gram of SiC

c. 20 mg of surfactant per gram of SiC

The results of the experiment are summarized in Table 1, which also gives the above-mentioned experimental conditions.

By the term "zeta-potential without surfactant" used in this table and also in other tables is meant the zeta-potential which was measured with the dispersion which exclusively contained the respective inorganic particles and demineralized water.

As is shown by Table 1, the use of 5 and 10 mg of surfactant per gram of particles resulted in incorporating only a small amount of SiC, which moreover was not homogeneously distributed in the nickel. The zeta-potentials in the corresponding 0.005 N KNO3 -solutions were below +40 mV and were -25 and +12 mV, respectively. It was also found that during the dispersing of the electrolyte, the particles and the surfactant, using 5 and 10 mg of surfactant per gram of SiC, respectively, a flocculent mixture was formed.

Both quantitatively and qualitatively the incorporation was considerably better when use was made of 20 mg of surfactant per gram of particles having a zero-potential of +76 mV. The volume percentage of the incorporated SiC particles was 57, and the particles were homogeneously distributed in the nickel.

EXAMPLE II

The procedure used in Example I was repeated with SiC particles having a size of about 15 μm and supplied by the Dutch firm of Norton at Rotterdam under the name SiC 500. The conditions and the results are given in Table 2.

EXAMPLE III

In the experiment on which this example is based, the solid inorganic particles were of B4 C. Particles of this boron carbide having a particle size of about 2 μm, known under the name B4 C1500, had been obtained from the German firm of Kempten GmbH, Munich.

Use was made of a nickel sulfamate bath and a different cationic fluorocarbon surfactant from the one used in Examples I and II. The surfactant of this Example II had as the structural formula ##STR4##

Further conditions and the results of this experiment are included in Table 3. The table shows that under the given conditions the particles were quite satisfactorily incorporated, both quantitatively and qualitatively, also when use was made of boron carbide.

EXAMPLE IV

In this example, use was made of solid inorganic MoSi2 particles supplied by the firm of Starck at West-Berlin. The bath was again a Watt's nickel plating bath and the surfactant again of the type used in the Examples I and II. Additional data are mentioned in Table 4. Also in this experiment, both a qualitatively and quantitatively satisfactory incorporation of particles was obtained.

EXAMPLE V

The material of the solid inorganic particles in this experiment was a diamond powder supplied by the Swiss firm of Rudolf Spring A. G. under the name Diamond grade 3. Use was made of a nickel sulfamate bath and the same type of surfactant as employed in Example III. Table 5 gives further particulars about the conditions used in and the results obtained by the experiment. Considering the relatively small concentration of diamond powder (as little as 20 g/liter bath liquid) a remarkably high percentage of incorporated diamond powder was reached (28%) compared with the percentage obtained with the known electroplating process for deposition of metals and diamond powder.

EXAMPLE VI

In the experiment relating to this example, the solid inorganic substance consisted of chromium powder having a particle size of about 2 μm. The powder had been supplied by the American firm of Alfa Products at Danvers. The experiment was again carried out in a Watt's nickel plating bath, use being made of the same surfactant as in Example I. The conditions and the results of the experiment are given in Table 6. The composite layer contained 47 percent by volume of chromium powder which was homogeneously distributed in it. When this experiment was carried out in accordance with the procedure described in British Patent Specification No. 1,070,343, using as surfactant n-hexadecyltrimethyl ammonium bromide (CTAB) (a nonfluorocarbon-containing surfactant) the zeta potential was found to have a value not exceeding +20 mV. The particles were not homogeneously distributed over the surface.

The resulting coating was black and had a poor appearance.

In the following three comparative examples use was made, as in Example I, of a Watt's nickel plating bath containing dispersed silicon carbide particles referred to as SiC1200. However, instead of with a cationic fluorocarbon surfactant, the treatment was carried out in the presence of cationic hydrocarbon surfactants.

EXAMPLE VII

The cationic hydrocarbon surfactant had the following structural formula: ##STR5## The conditions and results of the experiments are shown in Table 7.

EXAMPLE VIII

The cationic surfactant used here had the following structural formula: ##STR6##

Additional data are mentioned in Table 8.

EXAMPLE IX

In the experiment carried out according to this example use was made of a cationic surfactant having the structural formula: ##STR7##

Table 9 gives additional data on experimental conditions and results.

Although in all the comparative Examples VII-IX, the zeta potential can be seen to lie above the set lower limit of +40 mV, the use of a cationic surfactant which is not of the fluorocarbon type results in the incorporation of a considerably smaller amount of SiC than is the case in Example I for a zero-potential of +76 mV (0, 12 and 10 percent by volume in the Examples VII, VIII and IX, respectively, against 57 percent by volume in Example I).

EXAMPLE X

In the experiment according to this example, use was made of a mixture of two inorganic substances. One substance was SiC1200, as employed in Example VIII. The other substance was molybdenum disulphide having a particle size of about 25 μm. It had been obtained from the Swiss firm of Fluka A. G.

The experiment was again carried out in a Watt's nickel plating bath, use being made of the same surfactant as in Example I. In table 10, the conditions used and the results obtained are summarized. The composite layer contained 27 percent by volume of silicon carbide and 18 percent by volume of molybdenum disulphide. Both substances were homogeneously distributed in the metal coating.

Although the invention has been described in detail for the purposes of illustration, it is to be understood that such detail is solely for the purpose of illustration and that variations can be made therein without departing from the spirit and scope of the invention except as it may be limited by the claims.

                                  TABLE 1__________________________________________________________________________Inorganic    supplier     Kempten GmbHparticles    particle size                 about 5 μm    density      3.25 g/cm3    specific surface area                 about 2 m2 /gsilicium-    zeta potential withoutcarbide  surfactant   -57 mV("Sic 1200")    zeta potential with    surfactant in a concentra-    tion of    a. 5 mg per g of particles                 -25 mV    b. 10 mg per g of particles                 +12 mV    c. 20 mg per g of particles                 +76 mV    content in the bath                 50 g/literSurfactant    type         cationic, FC-type    structure                  ##STR8##    content relative to the    inorganic particles                 a. 5 mg surf./gram of particles                 b. 10 mg surf./gram of particles                 c. 20 mg surf./gram of particleselectrolytebath     NiSO4 . 6 H2 O                 240 g/l    NiCl2 . 6 H2 O                 40 g/l    H3 BO3                 40 g/lWatt's nickelplating bath    pH           4.2    temperature  52 C.    bath vessel  2000 ml-beaker    anode        bent nickel plate    cathode      stainless steel bar, 4mm,                 diam., 60 mm long    current density                 10 A/dm2    bath agitation                 moderate (with magnetic                 stirrer)    electroplating time                 15 minutesdispersing of    stirrer      Ultra Turraxmixture, stirrer speed                 10 0000 r.p.m.electrolyte,    stirring time                 1 minuteparticles and    rating of mixture with:surfactant    a. 5 mg surf. per g of part                 flocculent    b. 10 mg surf. per g of part                 very flocculent    c. 20 mg surf. per g of part                 homogeneous and stablecomposite    volume percentage/distri-coating of nickel    bution of incorporatedand SiC particles    particles with:    a. 5 mg surf. per g of part                 9%/inhomogeneous    b. 10 mg surf. per g of part                 4%/inhomogeneous    c. 20 mg surf. per g of part                 57%/homogeneous    coating thickness                 30 μm__________________________________________________________________________

              TABLE 2______________________________________Inorganic    supplier         Norton, Rotterdamparticles    particle size    about 15 μm    density          3.25 g/cm3    specific surface area                     about 0.7 m2 /gSilicium zeta potential without                     -38 mVcarbide  surfactant("SiC 500")    zeta potential with sur-                     +65 MV    factant in a concentra-    tion of 25 mg per g of    particles    content in the bath                     35 g/ litersurfactant    type             Same as in Table 1    structure    content relative to                     25 mg of surfactant/    the inorganic particles                     gram of particleselectrolyte    NiSO4 . 6 H2 O                     240 g/lbath     NiCl2 . 6 H2 O                     40 g/l    H3 BO3 40 g/lWatt's nickel    pH               4,1plating bath    temperature      50 C.    bath vessel      1500 ml-beaaker    anode            nickel grains in bag    cathode          stainless steel bar 4 mm                     diam, 60 mm long    current density  5 A/dm2    bath agitation   moderate    electroplating time                     150 minutesdispersing of    stirrer          ultra Turraxmixture, stirrer speed    10 000 r.p.m.electrolyte,    stirrer time 4 minutesparticlesandsurfactantcomposite    volume percentage /coating of    distribution of in-nickel and    corporated particlesSiC particles    with 25 mg of sur-    factant per g of    particles        40%/homogeneous    coating thickness                     about 180 μm.______________________________________

                                  TABLE 3__________________________________________________________________________Inorganic    supplier     Kempten GmbHparticles    particle size                 about 2 μm    density      2.52 g/cm3    specific surface area                 about 6 m2 /gboron carbide    zeta-potential without("B4 C1500 ")    surfactant   -50 mV    zeta potential with sur-    factant in a concentration    of 50 mg per gramme of    particles    +72 mV    content in the bath                 30 g/lsurfactant    type         cationic FC-type    structure                  ##STR9##    content relative to the                 50 mg surf./gram of particles    inorganic particleselectrolyte    Ni (NH2 SO3)2                 460 g/lbath     NiCl2   5 g/l    H3 BO3                 40 g/lnickel sulfamate    pH           4.1bath     temperature  55 C.    bath vessel  2000 ml-beaker    anode        bent nickel plate    cathode      stainless steel bar 4 mm in                 diam., 60 mm long    current density                 15 A/dm2    bath agitation                 moderate (with magn. stirrer)    electroplating time                 15 minutesdispersing of    stirrer      Ultra Turraxmixture, electro-    speed of stirrer                 10 000 r.p.m.lyte, particles    stirring time                 2 minutesand surfactantcomposite coating    volume percentage/dis-of nickel and    tribution of incorporatedB4 C particles    particles with 50 mg of    surf. per g of particles                 45%/homogeneous    coating thickness                 50 μm__________________________________________________________________________

              TABLE 4______________________________________Inorganic  supplier      Starck, Berlinparticles  particle size 5 to 6 μm      density       abt 6.2 g/cm3      specific surface      area          abt 1.5 m2 /gMoSi2 zeta-potential with      surfactant in a con-      centration of 30 mg      per gramme of      particles content in                    abt +60 mV      the bathsurfactant type          Same as in Table 1      structure      content       30 mg of surf./gram      relative to the                    of particles      inorganic particleselectrolytebath       NiSO4 . 6H2 O                    240 g/l      NiCl2 . 6 H2 O                    40 g/l      H3 BO3                    40 g/l      pH            4.1      temperature   55 C.Watt's nickel      bath vessel   2000 ml-beakerplating bath      anode         bent nickel plate      cathode       stainless steel bar,                    4 mm diam., 60 mm long      current density                    5 A/dm2      bath agitation                    moderate (with magnetic      electroplating time                    stirrer) 60 minutesdispersing of mix-      stirrer       Ultra Turraxture, electrolyte      stirrer speed 10 000 r.p.m.particles and      stirring time 2 minutessurfactantcomposite coating      volume percentage/of nickel and      distribution ofmolybdenum incorporated par-silicide   ticles with 30 mg      of surfactant per      g of particles                    32%/homogeneous      coating thickness                    about 60 μm______________________________________

              TABLE 5______________________________________Inorganic  supplier         Rudolf Spring                       A.G.particles  particle size    2 to 4 μm      density          3.25 g/cm3      specific surface area                       3.9 m2 /g      zeta-potential withoutDiamond    surfactant       -38 mVgrade 3    zeta-potential with sur-      factant in a concentration      of 20 mg per gramme of      particles        +65 mV      content in the bath                       20 g/lsurfactant type             as in Table 3      structure      content relative to the                       20 mg of sur-      inorganic particles                       factant per                       g of particleselectrolyte      Ni(NH2 SO3)2                       460 g/lbath       NiCl2       5 g/l      H3 BO3 40 g/l      pH               4.1nickel sulfamate      temperature      55 C.bath       bath vessel      2000 ml-beaker      anode            bent nickel plate      cathode          stainless steel bar,                       4 mm in                       diam., 60 mm long      current density  10 A/dm2      bath agitation   moderate (with                       magnetic stirrer)      electroplating time                       15 minutesdispersing of      stirrer          Ultra Turrax -mixture, stirrer speed 10 000                       r.p.m.electrolyte,      stirring time    2 minutesparticles andsurfactantcomposite  volume percentage/coating of nickel      distribution of the in-and diamond      corporated particles withpowder     20 mg of surfactant per      g of particles   28%/      coating thickness                       homogeneous                       about 30 μm______________________________________

              TABLE 6______________________________________Inorganic  supplier        Alfa Productsparticles  particle size   about 2 μm      density         7.1 g/cm3      specific surface area                      0.85 m2 /gchromium powder      zeta-potential without      surfactant      -35 mV      zeta-potential with      surfactant      in a concentration      of 25 mg per gramme of      particles       +55 mV      content in the bath                      50 g/lSurfactant type            as in Table 1      structure      content relative to                      25 mg of surfactant      the inorganic particles                      per 1 g of particleselectrolyte      NiSO4 . 6 H2 O                      240 g/lbath       NiCl2 . 6 H2 O                      40 g/l      H3 BO3                      40 g/l      pH              4.1Watt's nickel      temperature     50 C.plating bath      bath vessel     2000 ml-beaker      anode           bent nickel plate      cathode         stainless steel bar,                      4 mm in diam,                      60 mm long      current density 5 A/dm2      bath agitation  moderate (with                      magnetic stirrer)      electroplating time                      50 minutesdispersing of mix-      stirrer         Ultra Turraxture, electrolyte,      stirrer speed   10 000 r.p.m.particles and      stirring time   11/2  minutessurfactantcomposite coating      volume percentage/of nickel  distribution ofand chromium      incorporated particlespowder     with 25 mg of surfactant      per 1 g of particles                      47%/homogeneous      coating thickness                      about 52 μ______________________________________

                                  TABLE 7__________________________________________________________________________Inorganic  supplier    Kempten G.m.b.H.particles  particle size                  about 5 μm      density     3.25 g/cm3      specific surface area                  about 2 m2 /gsilicium   zeta-potential withoutcarbide    surfactant  -57 mV("SiC 1200")      zeta-potential with      surfactant in a      concentration of 30 mg      per 1 gramme of      particles   +65 mV      content in the bath                  50 g/lSurfactant type        cationic CH-type      structure                   ##STR10##                   ##STR11##      content relative to      the inorganic particles                  30 mg of surfactant per 1 g                  of particleselectrolyte bath      Ni (NH2 SO3)2                  460 g/l      NiCl2  5 g/l      H3 BO3                  40 g/l      pH          4.2Nickel sulfamate      temperature 55 C.bath       bath vessel 2000 ml-beaker      anode       nickel plate      cathode     stainless steel bar, 4 mm in                  diam., 60 mm long      current density                  15 A/dm2      bath agitation                  moderate (with magnetic                  stirrer)      electroplating time                  15 minutesdispersing of mixture,      stirrer     Ultra Turraxelectrolyte, particles      stirrer speed                  10 000 r.p.m.and surfactant      stirring time                  2 minutes      rating of mixture with      30 mg of surfactant per      1 g of particles                  very flocculentcomposite coating      volume percentage/of nickel and      distribution of thesilicium carbide      incorporated particles      with 30 mg of surfactant      per 1 g of particles                  0%      coating thickness                  about 50 μm__________________________________________________________________________

                                  TABLE 8__________________________________________________________________________Inorganic    supplier      Kempten GmbHparticles    particle size about 5 μm    density       3.25 g/cm3    specific surface area                  about 2 m2 /g    zeta-potential without    surfactant    -57 mVsilicium zeta-potential with sur-carbide  factant in a concentration("SiC1200 ")    of 30 mg per 1 gramme    of particles  +90 mV    content in the bath                  50 g/lSurfactant    type          cationic, CH-type    structure                  C16 H33 --SO2 --NH--(CH2)3                   --.sup.⊕N--(CH3)3                  CH3 O--SO3    content relative to the    inorganic particles                  30 mg of surfactant per 1 g of                  particleselectrolytebath     Ni(NH2 SO3)2                  460 g/l    NiCl2    5 g/l    H3 BO3                  40 g/l    pH            4.2nickel sulfamate    temperature   55 C.bath     bath vessel   2000 ml-beaker    anode         nickel plate    cathode       stainless steel bar, 4 mm                  in diam., 60 mm long    current density                  15 A/dm2    bath agitation                  moderate (magnetic stirrer)    electroplating time                  2 minutesdispersing of    stirrer       Ultra Turraxmixture, elec-    stirrer speed 10,000 r.p.m.trolyte, particles    stirring time                  2 minutesand surfactant    rating of mixture with    30 mg of surfactant per    1 gramme of particles                  slightly flocculentcomposite coating    volume percentage/of nickel and    distribution of in-silicium carbide    corporated particles    with 30 mg of surfactant                  12%/inhomogeneous    per 1 gramme of particles    coating thickness                  50 μm__________________________________________________________________________

                                  TABLE 9__________________________________________________________________________Inorganic    supplier    Kempten GmbHparticles    particle size                about 5 μm    density     3.25 g/cm3    specific surface area                about 2 m2 /gsilicium zeta-potential withoutcarbide  surfactant  -57 mV("SiC1200 ")    zeta-potential with    surfactant in a con-    centration of 30 mg per    1 gramme of particles                +50 mV    content in the bath                50 g/lSurfactant    type        cationic, CHtype    structure                 ##STR12##                 ##STR13##    content relative to the                30 mg of surfactant per    inorganic particles                1 g of particleselectrolytebath     Ni(NH2 SO3)2                460 g/l    NiCl2  5 g/l    H3 BO3                40 g/l    pH          4.2nickel   temperature 55 C.sulfamate bath    bath vessel 2000 ml-beaker    anode       nickel plate    cathode     stainless steel bar 4 mm in                diam. 60 mm long    current density                15 A/dm2    bath agitation                moderate (magn. stirrer)    electroplating time                15 minutesdispersing of    stirrer     Ultra Turraxmixture, stirrer speed                10 000 r.p.m.electrolyte,    stirring speed                2 minutesparticles and    rating of mixturesurfactant    with 30 mg of sur-    factant per 1 gramme    of particles                slightly flocculentcomposite coating    volume percentage/of nickel and    distribution of thesilicium carbide    incorporated particles    with 30 mg of surfac-                10%/inhomogeneous    tant per 1 g of    particles    coating thickness                50 μm__________________________________________________________________________

                                  TABLE 10__________________________________________________________________________Inorganic    supplier of MoS2                  Fluka A.G.particles    particle size abt 25 μm    density       4.8 g/cm3    specific surface area                  0.5 m2 /gsilicium zeta-potential withoutcarbide  surfactant    of SiC        -55 mV    of MoS2  not measurable (stronglyas in example VIII    with surfactant in a                  hydrophobic)and MoS2    concentration of    25 mg per g SiC                  +65 mV    25 mg per g MoS2                  +55 mV    content in the bath                  25 g/l SiC and 25 g/l MoS2Surfactant    type          cationic, FC-type    structure                   ##STR14##    content relative to the                  both for SiC and    inorganic particles                  MoS2 25 mg/lelectrolyte    NiSO4 . 6 H2 O                  240 g/l    NiCl2 . 6 H2 O                  40 g/l    H3 BO3                  40 g/l    pH            4.2Watt's nickel    temperature   52  C.plating bath    bath vessel   2000 ml-beaker    anode         bent nickel plate    cathode       stainless steel bar, 4 mm                  in diam. 60 mm long    current density                  7.5 A/dm2    bath agitation                  moderate (with magnetic                  stirrer)    electroplating time                  30 minutesdispersing of mix-    stirrer       Ultra Turrax (the twoture, electrolyte      substances at once)particles and    stirrer speed 10 000 r.p.m.surfactant    stirring time 2 minutescomposite coating    volume percentage/                  SiC : 27 volume %of nickel and    distribution of incorporated                  MoS2 : 13 volume %chromium powder    particles with                  both substances were    25 mg/g for the two types                  homogeneously distributed    of particles  within each other    coating thickness                  about 45 μm__________________________________________________________________________
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Classifications
U.S. Classification205/50, 204/490, 205/109, 205/274, 205/273, 204/499
International ClassificationC25D15/02
Cooperative ClassificationC25D15/02
European ClassificationC25D15/02